US20070006529A1 - Compact steam reformer - Google Patents
Compact steam reformer Download PDFInfo
- Publication number
- US20070006529A1 US20070006529A1 US11/514,537 US51453706A US2007006529A1 US 20070006529 A1 US20070006529 A1 US 20070006529A1 US 51453706 A US51453706 A US 51453706A US 2007006529 A1 US2007006529 A1 US 2007006529A1
- Authority
- US
- United States
- Prior art keywords
- evaporator
- reactor
- steam reformer
- follow
- pipe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000446 fuel Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002485 combustion reaction Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000003380 propellant Substances 0.000 claims description 3
- 238000000629 steam reforming Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 17
- 238000004140 cleaning Methods 0.000 abstract description 6
- 239000003345 natural gas Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 33
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- 239000000567 combustion gas Substances 0.000 description 5
- 238000002407 reforming Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- YYAVXASAKUOZJJ-UHFFFAOYSA-N 4-(4-butylcyclohexyl)benzonitrile Chemical compound C1CC(CCCC)CCC1C1=CC=C(C#N)C=C1 YYAVXASAKUOZJJ-UHFFFAOYSA-N 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 201000003034 pontocerebellar hypoplasia type 4 Diseases 0.000 description 1
- 238000012802 pre-warming Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0496—Heating or cooling the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0403—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
- B01J8/0407—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds
- B01J8/0415—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds the beds being superimposed one above the other
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0461—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds
- B01J8/0469—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds the beds being superimposed one above the other
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0492—Feeding reactive fluids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00026—Controlling or regulating the heat exchange system
- B01J2208/00035—Controlling or regulating the heat exchange system involving measured parameters
- B01J2208/00044—Temperature measurement
- B01J2208/00061—Temperature measurement of the reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
- B01J2208/00132—Tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
- B01J2208/00141—Coils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00194—Tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00203—Coils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00477—Controlling the temperature by thermal insulation means
- B01J2208/00495—Controlling the temperature by thermal insulation means using insulating materials or refractories
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00504—Controlling the temperature by means of a burner
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00539—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00716—Means for reactor start-up
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Definitions
- the invention relates to a compact steam reformer and a method for steam reformation.
- a compact steam reformer is known from DE 101 19 083 A1, in which the process water is essentially evaporated by means of the reformate to be cooled. The waste heat from the combustion is recovered by pre-warming the air. NOx formation is avoided by employing the flameless oxidation process.
- This reformer permits a rapid output regulation and has a degree of effectiveness of up to approximately 80%.
- the novel compact steam reformer ( 1 ) combines in one device the steam reformation of natural gas or other fuel, including subsequent cleaning of CO. Controlled catalytic CO cleaning is achieved by careful temperature control at the follow-up reactor ( 37 , 39 , 39 a ). Temperature control is made possible by means of pressure-controlled operation of the evaporator ( 24 ).
- the compact steam reformer in accordance with the invention has a reactor which is heated by means of a burner.
- a preheating device with a high rate of heat recovery is assigned to the burner. This increases the efficiency of the reforming process.
- the reformer furthermore has a follow-up reactor, which is designed for performing a shift reaction, follow-up oxidation and/or methane generation from the carbon monoxide portions contained in the raw reformate.
- the follow-up reactor is in a heat-exchanging connection with a pipe evaporator, which maintains the temperature of the follow-up reactor at a fixed level in a controlled manner. By means of this, the desired selectivity of the follow-up reaction is maintained, even in case of a load change.
- the pipe evaporator causes the evening-out of the temperature in the follow-up reactor in regard to time, as well as in regard to space.
- the flow of material in the pipe evaporator causes a heat transport in the follow-up reactor, so that the latter can be rapidly adapted to a load change. This applies in particular if the pipe evaporator and the follow-up reactor operate in accordance with a co-current flow.
- the temperature of the follow-up reactor is simultaneously fixed within such narrow limits that the CO content can be reduced to values of less than 50 ppm. Because of this, catalytic follow-up treatment, filtering or other follow-up treatment of the process gas becomes superfluous.
- the gas generated by the compact steam reformer can be directly conducted to hydrogen fuel cells.
- the temperature of the follow-up reactor can be set in the simplest way by the regulation of the steam pressure.
- the steam generation temperature for all operational states is simultaneously fixed, along with the steam pressure.
- the close thermal connection between the follow-up reactor and the pressure-regulated evaporator for example by means of the embodiment of the pipe evaporator as a pipe coil and the arrangement of possible catalyzers in the spaces between the pipes, creates favorable conditions for the generation of low-CO hydrogen.
- the compact steam reformer can have a jet pump connected to the pipe evaporator or other evaporator, which generates a fuel—steam mixture of a preselected composition and feeds the reactor.
- a jet pump connected to the pipe evaporator or other evaporator, which generates a fuel—steam mixture of a preselected composition and feeds the reactor.
- This provides the basis for a particularly simple control of the compact steam reformer by means of control techniques.
- the amount of steam is controlled by an appropriate metering of feed water amounts.
- the amount of fuel supplied to the reformer for reforming need not be separately controlled and is instead metered in by the jet pump.
- FIG. 1 is a compact steam reformer with an attached fuel cell in a schematic representation
- FIG. 2 is the temperature profile of the process gases in the form of a diagram
- FIG. 3 is the temperature profile of the heating gases in the form of a diagram
- FIG. 4 is the compact steam reformer in schematic longitudinal section with the allocation of its work zones to the diagrams in accordance with FIGS. 2 and 3 .
- a steam reformer 1 is represented in longitudinal section in FIG. 1 . It has an outer shell 2 of a length L and circular cross section of a diameter D. It can be cylindrical, or also stepped in the form of several cylinders. All connectors 3 are preferably conducted through its upper end 4 .
- a reformer pipe 5 closed at the bottom, is arranged concentrically inside the shell 2 and at a distance from it.
- the annular space provided between the shell 2 and the reformer pipe 5 is filled with an insulating material 6 for thermal insulation.
- a feed line 7 for a mixture of fuel and steam leads from the upper end 4 , extending initially straight and then downward by means of turns through the insulating material 6 to a feed connector 8 at the lower end of the reformer pipe 5 .
- the lower, cup-shaped end of the latter constitutes the outer shell of a reactor 9 for performing the actual reforming process.
- the reactor 9 is delimited by an inner reformer pipe 11 , which is closed off in a cup shape at the bottom and is maintained on the end 4 at the top.
- a catalyzer 12 for the reforming process is arranged in the cup-shaped annular space between the lower end of the inner reformer pipe 11 and the lower end of the outer reformer pipe 5 .
- the reformer pipe 11 is provided with ribs 13 , 14 on the inside as well as on the outside, which are used for heat transfer between the catalyzer 12 and a combustion chamber 15 , which is enclosed by the reformer pipe 11 .
- a burner 16 is assigned to the combustion chamber and is used for heating the catalyzer 12 and is designed to create a flameless oxidation of the fuel introduced into the combustion chamber 15 .
- a number of gas and air nozzles 17 , 18 is provided for this purpose, which are arranged, aligned in the same direction, in a ring and create a large-volume circulation.
- a hollow-cylindrical guide body 19 which is arranged concentrically with the ring of nozzles can assist the large-volume circulation, which is indicated by arrows in FIG. 1 .
- the gas nozzles 17 are fed via a preheating arrangement 20 , which utilizes waste heat. Parts of this are lines 21 , 22 , which are conducted in the form of coils through an exhaust gas conduit 23 formed inside the upper part of the reformer pipe 11 . In this way the combustion gas supplied to the combustion chamber 15 , as well as the supplied air, are preheated. A high recouperation degree, and therefore cool exhaust gas, is achieved.
- An ignition burner Z or an electric heating device can be centrally provided, which are used for preheating the combustion chamber 15 until the start of the flameless oxidation.
- the steam reformer 1 so far described contains a steam generator 24 arranged in the annular space 10 between the outer recouperation pipe 5 and the inner recouperation pipe 11 and is coupled with them in a heat-technological manner.
- the steam generator 24 is constituted by a pipe coil, which is divided into several sections and is arranged concentrically in respect to the preheating device.
- a pipe 25 is arranged in-between, which encloses a further annular space 26 together with the inner reformer pipe 11 .
- This space is filled with an insulating material 27 for the thermal insulation of the exhaust gas conduit 23 from the reformate conduit, which is formed between the outer reformer pipe 5 and the pipe 25 through the annular space 10 .
- the steam generator 24 has a feedwater connector 28 , starting from which a first pipe coil section 29 leads through the reformate conduit, which terminates at a reformate outlet 31 .
- the pipe coil section 29 constitutes a water/reformate counterflow radiator operating in a counterflow manner.
- the pipe coil 29 leads to a bridging pipe 32 , which leads through the space 26 in the axial direction. It then changes back into the outer annular space 10 constituting the reformat conduit, and is continued there as the pipe coil section 33 . It constitutes a water heater and simultaneously a reformate shock cooler (quench cooler, section A in FIGS. 3 and 5 ).
- a gas-permeable annular insulating body 34 is arranged between the pipe coil section 33 and the catalyzer 12 , which prevents overheating of the steam generator 24 when there is no load, i.e. in case of a feedwater flow-through of zero or close to zero.
- a further pipe coil section 35 follows the pipe coil section 33 and consists of several coils 36 , 38 (section B in FIGS. 3 and 5 ). These coils 36 , 38 have been embedded in a catalyzer, which also fills spaces between coils and constitutes a follow-up reactor.
- the first coils 36 have been embedded, for example, in a CO-shift catalyzer 37 .
- the subsequent coils 38 (section C in FIGS. 3 and 5 ) have been embedded in a methane-generating catalyst 39 .
- the catalysts 37 , 39 can be attached to a suitable catalyst body, such as a woven wire device or the like, for example, or also deposited as loose bulk material between the coils 36 , 38 , or can be directly formed on the ribs of an evaporator embodied as a ribbed pipe.
- a suitable catalyst body such as a woven wire device or the like, for example, or also deposited as loose bulk material between the coils 36 , 38 , or can be directly formed on the ribs of an evaporator embodied as a ribbed pipe.
- the evaporator 24 is divided into three sections A, B, C, namely the pipe coil section 33 for the at least partial evaporation of the water and shock cooling of the reformats, as well as the sections constituted by the coils 36 and 38 , in which the further, to a large extent complete evaporation of the water is provided by heat exchange with the respective catalyzers 37 , 39 .
- the catalysts 37 , 39 constitute the two-stage follow-up reactor.
- the outlet of the evaporator 24 is connected via an ascending pipe 41 with a pressure-control valve 42 , which maintains the pressure in the evaporator 24 constant, regardless of the flow through it.
- the steam emitted by the pressure-control valve 42 is conducted to the propellant nozzle connector 43 of a jet pump 44 , whose suction connector 45 is connected to a fuel feed line. Its outlet feeds a mixture of steam and fuel to the feed line 7 .
- the feedwater connector 28 is provided with feedwater by a feedwater pump 46 .
- the latter is controlled or regulated by a control device 47 on the basis of a temperature of the catalyzer 12 detected by means of a temperature sensor 48 in such a way, that the temperature of the catalyzer 12 is kept constant. Since the air requirement for the burner and the fuel cell are proportional to the energy supply PCH4, and therefore the feedwater temperature, the regulation ratio of the air blower 49 can track in a simple manner the regulation ratio of the feedwater pump 46 , which is specified by the control device 47 .
- Air and combustion gas are supplied via the lines 21 , 22 .
- the residue gas from the anode of a fuel cell can be used as the combustion gas.
- the reformate is conducted to an anode input of a fuel cell 52 .
- Residue gas generated by the anode is conducted via a line 53 to the preheating arrangement 20 .
- the blower 49 conveys air to the cathode of the fuel cell and to the preheating arrangement 20 .
- FIG. 3 illustrates the temperature of the gases supplied via the lines 21 , 22 , namely air and combustion gas.
- the branch II of the curve illustrates the exhaust gas temperature of the exhaust gas conducted out in counterflow.
- the represented temperatures reflect the temperature profile in the steam reformer 1 illustrated in FIG. 4 , in particular in its recouperator.
- the loop-shaped branch III of the curve in FIG. 3 represents the temperature in the combustion chamber 15 in the course of the flameless oxidation. As represented, the gas performs several revolutions through the combustion chamber 15 .
- an exhaust gas temperature of, for example, 150° C., to attain an air and gas preheating up to approximately 800° C.
- the curve in FIG. 2 represents the temperature profile of the gas to be reformed and already reformed.
- the branch IV of the curve indicates the heating of the feedwater in the pipe coil section 29 , which is simultaneously a feedwater preheater and a water reformate counterflow cooler.
- the feedwater which is under pressure and preheated, is conducted to the evaporator 24 at a temperature of slightly above 100° C. Initially, this is symbolized by the lower horizontal branch V of the curve.
- the preheated feedwater enters the evaporator at a point VI. It is brought to the evaporation temperature (curve VIII) in the pipe coil section 33 , and then passes through the entire evaporator 24 , in which it slowly evaporates.
- the pipe evaporator 24 sets a uniform temperature for the follow-up reactor.
- the evaporation temperature T s is not exceeded.
- the size of the evaporator temperature is set by means of the evaporator pressure at the pressure-control valve 42 .
- the temperature profile in accordance with FIG. 2 is also maintained within narrow limits, even in case of load changes, in particular in the last stage.
- the selectivity of the follow-up reaction is maintained in this way.
- the temperature setting in the last follow-up reactor stage is here effected solely by pressure control.
- the generated steam reaches the jet pump 44 .
- the latter fixes the steam/fuel ratio by means of its ratio between the propellant nozzle diameter and the mixing nozzle diameter.
- the jet pump 44 aspirates the desired amount of fuel via its suction connector 45 and mixes it with steam.
- the steam temperature initially slightly drops ( FIG. 2 , branch XI of the curve), wherein the temperature of the admixed combustion gas suddenly rises (branch X of the curve). Then the temperature slowly rises until the feed connector 8 is reached (branch XI of the curve).
- the temperature of the curve continues to increase in accordance with the branch XII until it reaches the temperature T R , which has been detected by the temperature sensor 49 and is constantly regulated by metering in feedwater.
- the reformate generated by the catalyzer 12 leaves the reactor 9 at this temperature.
- the reformate is shock-cooled ( FIG. 2 , branch XIII of the curve) as section A.
- the steam reformer 1 so far described operates inherently stably.
- An increased reduction of the electrical output Pe 1 worsens the caloric value of the residue gas from the anode.
- the control device increases the feedwater conveyance and therefore the steam generation and the reformate generation.
- the resultant increase of residue gas from the anode increases the burner output in the combustion chamber 15 . In this way the steam reformer 1 performs an automatic matching to the load.
- the losses of the reformate which can be affected are respectively proportional Delta T w (Delta T w is the difference between wall temperature and ambient temperature), Delta T 2 and Delta T R (see FIG. 2 ). They are furthermore a function of the excess steam in the reformate, which is necessary for soot-free reforming and the shift reaction.
- the novel compact steam reformer 1 combines in one device the steam reformation of natural gas or other fuel, including subsequent cleaning of CO. Controlled catalytic CO cleaning is achieved by careful temperature control at the follow-up reactor 37 , 39 , 39 a. Temperature control is made possible by means of pressure-controlled operation of the evaporator 24 .
Abstract
Description
- This is a continuation-in-part application of international application PCT/EP2005/002194 filed Mar. 2, 2005, and claiming the priority of
German application 10 2004 010 910.9 filed Mar. 6, 2004. - The invention relates to a compact steam reformer and a method for steam reformation.
- In the course of steam reforming hydrocarbons for the generation of hydrogen, the material flow for gas generation and the material flow for heating are kept separately in contrast to auto-thermal reforming. In this way the dilution of the hydrogen with nitrogen from the combustion air is avoided during steam reforming.
- A compact steam reformer is known from DE 101 19 083 A1, in which the process water is essentially evaporated by means of the reformate to be cooled. The waste heat from the combustion is recovered by pre-warming the air. NOx formation is avoided by employing the flameless oxidation process. This reformer permits a rapid output regulation and has a degree of effectiveness of up to approximately 80%.
- A similar reformer is known from WO 02/085781, which is optimized in respect to its exterior insulation.
- These reformers meet the intended expectations. However, there is the desire for further improvements in regard to the simplification of the process regulation and the efficiency of the heat recovery. Moreover, the reformate must be relieved as much as possible of the addition of CO. This must take place so completely that downstream connected CO-sensitive fuel cells are not damaged.
- It is known from
EP 1 031 374 A2 to place the CO containing process gas into a so-called CO oxidator, which is simultaneously used as a reformate cooler. Cooling is achieved by evaporating the inflowing process gas in an evaporator. - Based on the foregoing, it is the object of the invention to improve the compact steam reformer mentioned at the outset in regard to the conduct of the process and the efficiency of the heat recovery.
- This object is attained by means of the compact steam reformer in accordance with the invention as hereinafter described.
- The novel compact steam reformer (1) combines in one device the steam reformation of natural gas or other fuel, including subsequent cleaning of CO. Controlled catalytic CO cleaning is achieved by careful temperature control at the follow-up reactor (37, 39, 39 a). Temperature control is made possible by means of pressure-controlled operation of the evaporator (24).
- The compact steam reformer in accordance with the invention has a reactor which is heated by means of a burner. A preheating device with a high rate of heat recovery is assigned to the burner. This increases the efficiency of the reforming process. The reformer furthermore has a follow-up reactor, which is designed for performing a shift reaction, follow-up oxidation and/or methane generation from the carbon monoxide portions contained in the raw reformate. The follow-up reactor is in a heat-exchanging connection with a pipe evaporator, which maintains the temperature of the follow-up reactor at a fixed level in a controlled manner. By means of this, the desired selectivity of the follow-up reaction is maintained, even in case of a load change. The pipe evaporator causes the evening-out of the temperature in the follow-up reactor in regard to time, as well as in regard to space. The flow of material in the pipe evaporator causes a heat transport in the follow-up reactor, so that the latter can be rapidly adapted to a load change. This applies in particular if the pipe evaporator and the follow-up reactor operate in accordance with a co-current flow.
- By means of the determination of the evaporator temperature, the temperature of the follow-up reactor is simultaneously fixed within such narrow limits that the CO content can be reduced to values of less than 50 ppm. Because of this, catalytic follow-up treatment, filtering or other follow-up treatment of the process gas becomes superfluous. The gas generated by the compact steam reformer can be directly conducted to hydrogen fuel cells.
- The temperature of the follow-up reactor can be set in the simplest way by the regulation of the steam pressure. The steam generation temperature for all operational states is simultaneously fixed, along with the steam pressure. Thus, the close thermal connection between the follow-up reactor and the pressure-regulated evaporator, for example by means of the embodiment of the pipe evaporator as a pipe coil and the arrangement of possible catalyzers in the spaces between the pipes, creates favorable conditions for the generation of low-CO hydrogen.
- The compact steam reformer can have a jet pump connected to the pipe evaporator or other evaporator, which generates a fuel—steam mixture of a preselected composition and feeds the reactor. This provides the basis for a particularly simple control of the compact steam reformer by means of control techniques. For example, the amount of steam is controlled by an appropriate metering of feed water amounts. The amount of fuel supplied to the reformer for reforming need not be separately controlled and is instead metered in by the jet pump.
- For a better understanding of the invention reference may be made to the accompanying exemplary embodiments of the invention illustrated in the drawings, in which:
-
FIG. 1 is a compact steam reformer with an attached fuel cell in a schematic representation; -
FIG. 2 is the temperature profile of the process gases in the form of a diagram; -
FIG. 3 is the temperature profile of the heating gases in the form of a diagram; and, -
FIG. 4 is the compact steam reformer in schematic longitudinal section with the allocation of its work zones to the diagrams in accordance withFIGS. 2 and 3 . - A
steam reformer 1 is represented in longitudinal section inFIG. 1 . It has anouter shell 2 of a length L and circular cross section of a diameter D. It can be cylindrical, or also stepped in the form of several cylinders. Allconnectors 3 are preferably conducted through its upper end 4. - A reformer pipe 5, closed at the bottom, is arranged concentrically inside the
shell 2 and at a distance from it. The annular space provided between theshell 2 and the reformer pipe 5 is filled with aninsulating material 6 for thermal insulation. A feed line 7 for a mixture of fuel and steam leads from the upper end 4, extending initially straight and then downward by means of turns through theinsulating material 6 to afeed connector 8 at the lower end of the reformer pipe 5. The lower, cup-shaped end of the latter constitutes the outer shell of areactor 9 for performing the actual reforming process. Toward the inside, thereactor 9 is delimited by aninner reformer pipe 11, which is closed off in a cup shape at the bottom and is maintained on the end 4 at the top. Acatalyzer 12 for the reforming process is arranged in the cup-shaped annular space between the lower end of theinner reformer pipe 11 and the lower end of the outer reformer pipe 5. Preferably thereformer pipe 11 is provided withribs catalyzer 12 and acombustion chamber 15, which is enclosed by thereformer pipe 11. A burner 16 is assigned to the combustion chamber and is used for heating thecatalyzer 12 and is designed to create a flameless oxidation of the fuel introduced into thecombustion chamber 15. A number of gas and air nozzles 17, 18 is provided for this purpose, which are arranged, aligned in the same direction, in a ring and create a large-volume circulation. A hollow-cylindrical guide body 19, which is arranged concentrically with the ring of nozzles can assist the large-volume circulation, which is indicated by arrows inFIG. 1 . - The gas nozzles 17, as well as the air nozzles 18, are fed via a
preheating arrangement 20, which utilizes waste heat. Parts of this arelines reformer pipe 11. In this way the combustion gas supplied to thecombustion chamber 15, as well as the supplied air, are preheated. A high recouperation degree, and therefore cool exhaust gas, is achieved. Preferably (1-Delta T2/Delta T1)>greater than 0.8, wherein Delta T1 is the exhaust gas difference between the inlet and outlet of the exhaust gas conduit 23 of the preheatingarrangement 20, and Delta T2 is the difference between the exhaust gas temperature at the outlet and the fresh air temperature at the outlet. (1-Delta T2/Delta T1) is at least greater than 0.5. - An ignition burner Z or an electric heating device can be centrally provided, which are used for preheating the
combustion chamber 15 until the start of the flameless oxidation. - The
steam reformer 1 so far described contains asteam generator 24 arranged in theannular space 10 between the outer recouperation pipe 5 and theinner recouperation pipe 11 and is coupled with them in a heat-technological manner. Preferably thesteam generator 24 is constituted by a pipe coil, which is divided into several sections and is arranged concentrically in respect to the preheating device. A pipe 25 is arranged in-between, which encloses a furtherannular space 26 together with theinner reformer pipe 11. This space is filled with an insulatingmaterial 27 for the thermal insulation of the exhaust gas conduit 23 from the reformate conduit, which is formed between the outer reformer pipe 5 and the pipe 25 through theannular space 10. - The
steam generator 24 has a feedwater connector 28, starting from which a firstpipe coil section 29 leads through the reformate conduit, which terminates at a reformate outlet 31. Thepipe coil section 29 constitutes a water/reformate counterflow radiator operating in a counterflow manner. - The
pipe coil 29 leads to a bridgingpipe 32, which leads through thespace 26 in the axial direction. It then changes back into the outerannular space 10 constituting the reformat conduit, and is continued there as thepipe coil section 33. It constitutes a water heater and simultaneously a reformate shock cooler (quench cooler, section A inFIGS. 3 and 5 ). A gas-permeable annularinsulating body 34 is arranged between thepipe coil section 33 and thecatalyzer 12, which prevents overheating of thesteam generator 24 when there is no load, i.e. in case of a feedwater flow-through of zero or close to zero. - A further pipe coil section 35 follows the
pipe coil section 33 and consists of several coils 36, 38 (section B inFIGS. 3 and 5 ). Thesecoils 36, 38 have been embedded in a catalyzer, which also fills spaces between coils and constitutes a follow-up reactor. Here, the first coils 36 have been embedded, for example, in aCO-shift catalyzer 37. In the present exemplary embodiment the subsequent coils 38 (section C inFIGS. 3 and 5 ) have been embedded in a methane-generatingcatalyst 39. Thecatalysts coils 36, 38, or can be directly formed on the ribs of an evaporator embodied as a ribbed pipe. - In this way the
evaporator 24 is divided into three sections A, B, C, namely thepipe coil section 33 for the at least partial evaporation of the water and shock cooling of the reformats, as well as the sections constituted by thecoils 36 and 38, in which the further, to a large extent complete evaporation of the water is provided by heat exchange with therespective catalyzers catalysts - The outlet of the
evaporator 24 is connected via an ascending pipe 41 with a pressure-control valve 42, which maintains the pressure in theevaporator 24 constant, regardless of the flow through it. The steam emitted by the pressure-control valve 42 is conducted to the propellant nozzle connector 43 of ajet pump 44, whosesuction connector 45 is connected to a fuel feed line. Its outlet feeds a mixture of steam and fuel to the feed line 7. - The feedwater connector 28 is provided with feedwater by a
feedwater pump 46. The latter is controlled or regulated by acontrol device 47 on the basis of a temperature of thecatalyzer 12 detected by means of atemperature sensor 48 in such a way, that the temperature of thecatalyzer 12 is kept constant. Since the air requirement for the burner and the fuel cell are proportional to the energy supply PCH4, and therefore the feedwater temperature, the regulation ratio of theair blower 49 can track in a simple manner the regulation ratio of thefeedwater pump 46, which is specified by thecontrol device 47. - Air and combustion gas are supplied via the
lines - The reformate is conducted to an anode input of a
fuel cell 52. Residue gas generated by the anode is conducted via aline 53 to the preheatingarrangement 20. Theblower 49 conveys air to the cathode of the fuel cell and to the preheatingarrangement 20. - The steam reformer so far described operates as follows: Reference is made to FIGS. 2 to 4. Here, by means of a branch I of a curve,
FIG. 3 illustrates the temperature of the gases supplied via thelines steam reformer 1 illustrated inFIG. 4 , in particular in its recouperator. The loop-shaped branch III of the curve inFIG. 3 represents the temperature in thecombustion chamber 15 in the course of the flameless oxidation. As represented, the gas performs several revolutions through thecombustion chamber 15. As can be noted, it is possible at an exhaust gas temperature of, for example, 150° C., to attain an air and gas preheating up to approximately 800° C. - The curve in
FIG. 2 represents the temperature profile of the gas to be reformed and already reformed. The branch IV of the curve indicates the heating of the feedwater in thepipe coil section 29, which is simultaneously a feedwater preheater and a water reformate counterflow cooler. Now the feedwater, which is under pressure and preheated, is conducted to theevaporator 24 at a temperature of slightly above 100° C. Initially, this is symbolized by the lower horizontal branch V of the curve. The preheated feedwater enters the evaporator at a point VI. It is brought to the evaporation temperature (curve VIII) in thepipe coil section 33, and then passes through theentire evaporator 24, in which it slowly evaporates. In the course of this it retains its evaporation temperature of 200° C., for example, as illustrated by the horizontal branch VIII of the curve. In the same way as a heating pipe, thepipe evaporator 24 sets a uniform temperature for the follow-up reactor. The evaporation temperature Ts is not exceeded. The size of the evaporator temperature is set by means of the evaporator pressure at the pressure-control valve 42. - The temperature profile in accordance with
FIG. 2 is also maintained within narrow limits, even in case of load changes, in particular in the last stage. The selectivity of the follow-up reaction is maintained in this way. The temperature setting in the last follow-up reactor stage is here effected solely by pressure control. - From the
evaporator 24, the generated steam reaches thejet pump 44. The latter fixes the steam/fuel ratio by means of its ratio between the propellant nozzle diameter and the mixing nozzle diameter. Thejet pump 44 aspirates the desired amount of fuel via itssuction connector 45 and mixes it with steam. In the process the steam temperature initially slightly drops (FIG. 2 , branch XI of the curve), wherein the temperature of the admixed combustion gas suddenly rises (branch X of the curve). Then the temperature slowly rises until thefeed connector 8 is reached (branch XI of the curve). In thecatalyzer 12 the temperature of the curve continues to increase in accordance with the branch XII until it reaches the temperature TR, which has been detected by thetemperature sensor 49 and is constantly regulated by metering in feedwater. The reformate generated by thecatalyzer 12 leaves thereactor 9 at this temperature. When encountering the first section of the evaporator 24 (pipe coil section 33), the reformate is shock-cooled (FIG. 2 , branch XIII of the curve) as section A. - Thereafter, the cooled reformate reaches the
catalysts - The
steam reformer 1 so far described operates inherently stably. An increased reduction of the electrical output Pe1 worsens the caloric value of the residue gas from the anode. Thus, if the temperature at thetemperature sensor 49 drops, the control device increases the feedwater conveyance and therefore the steam generation and the reformate generation. The resultant increase of residue gas from the anode increases the burner output in thecombustion chamber 15. In this way thesteam reformer 1 performs an automatic matching to the load. - An actual embodied
steam reformer 1 has attained the following characteristic values:
Efficiency of the conversion into hydrogen when heating the reformer with residue gas from the anode: - Example of the novel reformer:
- -Exterior dimensions: L=0.6 m, D=0.3 m -Process gas: 1 m3/h natural gas of caloric value of 10 kWh/m3 -Water: 2.5 kg/h at 15 bar (=3 m3/h steam, S/C=3) -Heating gas: 0.41 m3/h natural gas of caloric value of 10 kWh/m3 -Reformate: 4 m3/H2 of caloric value of 3 kWh/m3 -Efficiency etaR=85%
When heating with residue gas from anode: (25% of H2 from the reformate, includes CH4 formed during methane generation) - -Available hydrogen: 2.7 m3/h of caloric value of 3 kWh/m3 -Efficiency etaR=81%
- The losses of the reformate which can be affected are respectively proportional Delta Tw (Delta Tw is the difference between wall temperature and ambient temperature), Delta T2 and Delta TR (see
FIG. 2 ). They are furthermore a function of the excess steam in the reformate, which is necessary for soot-free reforming and the shift reaction. - The novel
compact steam reformer 1 combines in one device the steam reformation of natural gas or other fuel, including subsequent cleaning of CO. Controlled catalytic CO cleaning is achieved by careful temperature control at the follow-upreactor evaporator 24.
Claims (19)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004010910.9 | 2004-03-06 | ||
DE102004010910A DE102004010910B4 (en) | 2004-03-06 | 2004-03-06 | Compact steam reformer |
PCT/EP2005/002194 WO2005084771A2 (en) | 2004-03-06 | 2005-03-02 | Compact steam reformer |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2005/002194 Continuation-In-Part WO2005084771A2 (en) | 2004-03-06 | 2005-03-02 | Compact steam reformer |
Publications (2)
Publication Number | Publication Date |
---|---|
US20070006529A1 true US20070006529A1 (en) | 2007-01-11 |
US7608120B2 US7608120B2 (en) | 2009-10-27 |
Family
ID=34877449
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/514,537 Expired - Fee Related US7608120B2 (en) | 2004-03-06 | 2006-09-02 | Compact steam reformer with automatic load matching capability |
Country Status (8)
Country | Link |
---|---|
US (1) | US7608120B2 (en) |
EP (2) | EP1732658B1 (en) |
JP (1) | JP4857258B2 (en) |
KR (1) | KR101202605B1 (en) |
CN (1) | CN100556527C (en) |
CA (1) | CA2557265C (en) |
DE (1) | DE102004010910B4 (en) |
WO (1) | WO2005084771A2 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090191436A1 (en) * | 2006-10-05 | 2009-07-30 | Wunning Joachim A | Fuel cell system |
WO2011080781A1 (en) | 2009-12-30 | 2011-07-07 | Hysytech S.R.L. | Endothermic reaction unit and steam reforming device comprising this reaction unit |
EP2534096A2 (en) * | 2010-02-13 | 2012-12-19 | McAlister Technologies, LLC | Chemical processes and reactors for efficiently producing hydrogen fuels and structural materials, and associated systems and methods |
EP2534097A2 (en) * | 2010-02-13 | 2012-12-19 | McAlister Technologies, LLC | Reactor vessels with pressure and heat transfer features for producing hydrogen-based fuels and structural elements, and associated systems and methods |
US10888833B2 (en) | 2016-03-23 | 2021-01-12 | Karlsruher Institut Fuer Technologie | Reactor for producing synthesis gas |
US10899612B2 (en) * | 2016-11-14 | 2021-01-26 | Korea Institute Of Energy Research | Hydrogen production reactor including carbon monoxide removing unit |
US11480364B2 (en) * | 2017-11-28 | 2022-10-25 | Anderson Industries, Llc | Flameless heater system to generate heat and humidity |
FR3129608A1 (en) * | 2021-11-30 | 2023-06-02 | Naval Group | REFORMER STRUCTURE |
Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100599735B1 (en) | 2004-11-29 | 2006-07-12 | 삼성에스디아이 주식회사 | Fuel cell system and reformer |
JP2007091584A (en) | 2005-09-27 | 2007-04-12 | Samsung Sdi Co Ltd | Fuel reforming apparatus |
DE102006039039A1 (en) * | 2006-05-23 | 2007-11-29 | Zentrum für Brennstoffzellen-Technik GmbH | Heating of a catalyst stage mounted downstream of a reformer, comprises feeding of air as heat transfer medium into the reformer through supply line, heating the fed medium by heater and thermally coupling the heated up medium in the stage |
JP5130684B2 (en) * | 2006-09-27 | 2013-01-30 | カシオ計算機株式会社 | Reaction apparatus and electronic equipment |
ATE470109T1 (en) | 2007-05-23 | 2010-06-15 | Ws Waermeprozesstechnik Gmbh | RECUPERATOR BURNER WITH FLATTENED HEAT EXCHANGER TUBES |
US9188086B2 (en) | 2008-01-07 | 2015-11-17 | Mcalister Technologies, Llc | Coupled thermochemical reactors and engines, and associated systems and methods |
US8441361B2 (en) | 2010-02-13 | 2013-05-14 | Mcallister Technologies, Llc | Methods and apparatuses for detection of properties of fluid conveyance systems |
KR20130036001A (en) | 2010-02-13 | 2013-04-09 | 맥알리스터 테크놀로지즈 엘엘씨 | Reactor vessel with transmissive surfaces for producing hydrogen-based fuels and structural elements, and associated systems and methods |
US9126831B2 (en) * | 2010-03-31 | 2015-09-08 | Council Of Scientific & Industrial Research | Hydrogen/syngas generator with sampling ports |
US8920732B2 (en) | 2011-02-15 | 2014-12-30 | Dcns | Systems and methods for actively controlling steam-to-carbon ratio in hydrogen-producing fuel processing systems |
DE102011013026A1 (en) | 2011-03-04 | 2012-09-06 | Dbi - Gastechnologisches Institut Ggmbh Freiberg | Process and arrangement for steam reforming of hydrocarbon gases |
CN103857873A (en) | 2011-08-12 | 2014-06-11 | 麦卡利斯特技术有限责任公司 | Systems and methods for extracting and processing gases from submerged sources |
US8911703B2 (en) | 2011-08-12 | 2014-12-16 | Mcalister Technologies, Llc | Reducing and/or harvesting drag energy from transport vehicles, including for chemical reactors, and associated systems and methods |
WO2013025655A2 (en) | 2011-08-12 | 2013-02-21 | Mcalister Technologies, Llc | Systems and methods for providing supplemental aqueous thermal energy |
WO2013025650A1 (en) | 2011-08-12 | 2013-02-21 | Mcalister Technologies, Llc | Mobile transport platforms for producing hydrogen and structural materials and associated systems and methods |
US8734546B2 (en) | 2011-08-12 | 2014-05-27 | Mcalister Technologies, Llc | Geothermal energization of a non-combustion chemical reactor and associated systems and methods |
US9522379B2 (en) | 2011-08-12 | 2016-12-20 | Mcalister Technologies, Llc | Reducing and/or harvesting drag energy from transport vehicles, including for chemical reactors, and associated systems and methods |
US9039327B2 (en) | 2011-08-12 | 2015-05-26 | Mcalister Technologies, Llc | Systems and methods for collecting and processing permafrost gases, and for cooling permafrost |
WO2014160301A1 (en) | 2013-03-14 | 2014-10-02 | Mcalister Technologies, Llc | Method and apparatus for generating hydrogen from metal |
US20150285534A1 (en) * | 2014-04-02 | 2015-10-08 | King Fahd University Of Petroleum And Minerals | Solar collector with optimal profile for energy distribution on a tubular receiver |
CN104226206A (en) * | 2014-07-28 | 2014-12-24 | 河北新启元能源技术开发股份有限公司 | Pressure difference reducing device using organic solvent to wash reactor |
DE102016208843A1 (en) * | 2016-05-23 | 2017-11-23 | Siemens Aktiengesellschaft | Reactor with a jet pump and method of increasing the pressure of a reactant with a jet pump |
CN106025448A (en) * | 2016-07-15 | 2016-10-12 | 郑州佛光发电设备有限公司 | Liquid pipeline built-in compact type aluminum-air fuel cell monomer |
CN106365118B (en) * | 2016-11-15 | 2018-09-14 | 晋城市阿邦迪能源有限公司 | Methanol steam reforming room with CO purifications and temp monitoring function |
US11285003B2 (en) | 2018-03-20 | 2022-03-29 | Medtronic Vascular, Inc. | Prolapse prevention device and methods of use thereof |
US11026791B2 (en) | 2018-03-20 | 2021-06-08 | Medtronic Vascular, Inc. | Flexible canopy valve repair systems and methods of use |
KR20220100350A (en) | 2021-01-08 | 2022-07-15 | 엘지전자 주식회사 | Reformer |
KR20220100351A (en) | 2021-01-08 | 2022-07-15 | 엘지전자 주식회사 | Reformer |
CN115650165A (en) * | 2022-11-15 | 2023-01-31 | 中国科学院大连化学物理研究所 | Fuel evaporation chamber structure used in cooperation with hydrogen production reformer of fuel cell |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5595833A (en) * | 1994-02-19 | 1997-01-21 | Rolls-Royce Plc | Solid oxide fuel cell stack |
US20020083829A1 (en) * | 1996-10-30 | 2002-07-04 | Edlund David J. | Hydrogen purification membranes, components and fuel processing systems containing the same |
US6641625B1 (en) * | 1999-05-03 | 2003-11-04 | Nuvera Fuel Cells, Inc. | Integrated hydrocarbon reforming system and controls |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3745047A (en) * | 1970-12-31 | 1973-07-10 | United Aircraft Corp | Proportional action electronic fuel control for fuel cells |
JPS5981416A (en) * | 1982-11-01 | 1984-05-11 | Yoshimitsu Sumiyoshi | Steam reforming method and device therefor |
JPS6270202A (en) * | 1985-09-19 | 1987-03-31 | Fuji Electric Co Ltd | Fuel reforming apparatus for fuel cell |
JPH09241002A (en) * | 1996-03-11 | 1997-09-16 | Fuji Electric Co Ltd | Fuel reformer for fuel cell power generator |
ATE275529T1 (en) * | 1996-06-28 | 2004-09-15 | Matsushita Electric Works Ltd | REFORMING DEVICE FOR PRODUCING A CRACKED GAS WITH REDUCED CO CONTENT. |
US6126908A (en) * | 1996-08-26 | 2000-10-03 | Arthur D. Little, Inc. | Method and apparatus for converting hydrocarbon fuel into hydrogen gas and carbon dioxide |
US5997594A (en) * | 1996-10-30 | 1999-12-07 | Northwest Power Systems, Llc | Steam reformer with internal hydrogen purification |
JPH10223244A (en) * | 1997-02-03 | 1998-08-21 | Fuji Electric Co Ltd | Fuel cell electricity generating apparatus |
DE19721630C1 (en) * | 1997-05-23 | 1999-02-11 | Fraunhofer Ges Forschung | Device for reforming hydrocarbons containing starting materials |
EP1138096B1 (en) * | 1998-10-14 | 2010-10-06 | IdaTech, LLC | Fuel processing system |
DE19907665C2 (en) | 1999-02-23 | 2003-07-31 | Ballard Power Systems | Device for utilizing heat generated during a catalytic reaction |
EP1094031A4 (en) * | 1999-04-20 | 2005-02-02 | Tokyo Gas Co Ltd | Single-pipe cylindrical reformer and operation method therefor |
AU768496B2 (en) * | 1999-05-03 | 2003-12-11 | Nuvera Fuel Cells | Autothermal reforming system with integrated shift beds, preferential oxidation reactor, auxiliary reactor, and system controls |
DE19954871A1 (en) * | 1999-09-07 | 2001-03-15 | Caloric Anlagenbau Gmbh | Hydrogen recovery from hydrocarbons involves steam reforming in presence of catalyst, separating hydrogen and recycling residual gas stream to reformer |
JP3903710B2 (en) * | 2000-07-25 | 2007-04-11 | 富士電機ホールディングス株式会社 | Fuel reformer and polymer electrolyte fuel cell power generator using the same |
DE10119083C1 (en) | 2001-04-19 | 2002-11-28 | Joachim Alfred Wuenning | Compact steam reformer |
JP2004059415A (en) * | 2002-06-03 | 2004-02-26 | Mitsubishi Heavy Ind Ltd | Fuel reformer and fuel cell power generation system |
JP2004031280A (en) * | 2002-06-28 | 2004-01-29 | Ebara Ballard Corp | Fuel processing device, fuel cell power generation system, fuel processing method and fuel cell power generation method |
JP4520100B2 (en) * | 2003-03-20 | 2010-08-04 | 新日本石油株式会社 | Hydrogen production apparatus and fuel cell system |
-
2004
- 2004-03-06 DE DE102004010910A patent/DE102004010910B4/en not_active Expired - Fee Related
-
2005
- 2005-03-02 KR KR1020067018135A patent/KR101202605B1/en active IP Right Grant
- 2005-03-02 EP EP05732059A patent/EP1732658B1/en not_active Expired - Fee Related
- 2005-03-02 JP JP2007502236A patent/JP4857258B2/en not_active Expired - Fee Related
- 2005-03-02 EP EP09156079A patent/EP2070591A3/en not_active Withdrawn
- 2005-03-02 WO PCT/EP2005/002194 patent/WO2005084771A2/en not_active Application Discontinuation
- 2005-03-02 CN CNB2005800071843A patent/CN100556527C/en not_active Expired - Fee Related
- 2005-03-02 CA CA2557265A patent/CA2557265C/en not_active Expired - Fee Related
-
2006
- 2006-09-02 US US11/514,537 patent/US7608120B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5595833A (en) * | 1994-02-19 | 1997-01-21 | Rolls-Royce Plc | Solid oxide fuel cell stack |
US20020083829A1 (en) * | 1996-10-30 | 2002-07-04 | Edlund David J. | Hydrogen purification membranes, components and fuel processing systems containing the same |
US6641625B1 (en) * | 1999-05-03 | 2003-11-04 | Nuvera Fuel Cells, Inc. | Integrated hydrocarbon reforming system and controls |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090191436A1 (en) * | 2006-10-05 | 2009-07-30 | Wunning Joachim A | Fuel cell system |
US8313867B2 (en) | 2006-10-05 | 2012-11-20 | Ws Reformer Gmbh | Fuel cell system |
WO2011080781A1 (en) | 2009-12-30 | 2011-07-07 | Hysytech S.R.L. | Endothermic reaction unit and steam reforming device comprising this reaction unit |
EP2534096A2 (en) * | 2010-02-13 | 2012-12-19 | McAlister Technologies, LLC | Chemical processes and reactors for efficiently producing hydrogen fuels and structural materials, and associated systems and methods |
EP2534097A2 (en) * | 2010-02-13 | 2012-12-19 | McAlister Technologies, LLC | Reactor vessels with pressure and heat transfer features for producing hydrogen-based fuels and structural elements, and associated systems and methods |
EP2534097A4 (en) * | 2010-02-13 | 2014-06-11 | Mcalister Technologies Llc | Reactor vessels with pressure and heat transfer features for producing hydrogen-based fuels and structural elements, and associated systems and methods |
EP2534096A4 (en) * | 2010-02-13 | 2014-06-11 | Mcalister Technologies Llc | Chemical processes and reactors for efficiently producing hydrogen fuels and structural materials, and associated systems and methods |
US10888833B2 (en) | 2016-03-23 | 2021-01-12 | Karlsruher Institut Fuer Technologie | Reactor for producing synthesis gas |
US10899612B2 (en) * | 2016-11-14 | 2021-01-26 | Korea Institute Of Energy Research | Hydrogen production reactor including carbon monoxide removing unit |
US11480364B2 (en) * | 2017-11-28 | 2022-10-25 | Anderson Industries, Llc | Flameless heater system to generate heat and humidity |
FR3129608A1 (en) * | 2021-11-30 | 2023-06-02 | Naval Group | REFORMER STRUCTURE |
Also Published As
Publication number | Publication date |
---|---|
CA2557265C (en) | 2012-10-30 |
KR101202605B1 (en) | 2012-11-19 |
EP2070591A3 (en) | 2009-08-26 |
CA2557265A1 (en) | 2005-09-15 |
EP1732658A2 (en) | 2006-12-20 |
JP4857258B2 (en) | 2012-01-18 |
JP2007527842A (en) | 2007-10-04 |
US7608120B2 (en) | 2009-10-27 |
WO2005084771A2 (en) | 2005-09-15 |
DE102004010910A1 (en) | 2005-09-22 |
KR20070019986A (en) | 2007-02-16 |
WO2005084771A3 (en) | 2005-12-01 |
EP2070591A2 (en) | 2009-06-17 |
CN100556527C (en) | 2009-11-04 |
EP1732658B1 (en) | 2011-09-14 |
CN1980732A (en) | 2007-06-13 |
DE102004010910B4 (en) | 2006-10-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7608120B2 (en) | Compact steam reformer with automatic load matching capability | |
US6835354B2 (en) | Integrated reactor | |
US7074373B1 (en) | Thermally-integrated low temperature water-gas shift reactor apparatus and process | |
EP0600621B1 (en) | A combined reformer and shift reactor | |
US6887285B2 (en) | Dual stack compact fuel processor for producing hydrogen rich gas | |
US7670394B2 (en) | Compact reforming reactor | |
KR101299170B1 (en) | Compact reforming reactor | |
US20150129805A1 (en) | Method for producing co and/or h2 in an alternating operation between two operating modes | |
EP1669133A1 (en) | Small cylindrical reformer | |
JP2010513834A (en) | Heat transfer unit for steam generation and gas preheating | |
US5651800A (en) | Reformer for fuel cell system | |
JP5154272B2 (en) | Fuel cell reformer | |
US20030188475A1 (en) | Dynamic fuel processor with controlled declining temperatures | |
JPH07101614B2 (en) | Fuel cell integrated with steam reformer | |
US20020090329A1 (en) | Apparatus for a fuel processing system | |
JP2817236B2 (en) | Methanol reforming reactor | |
EP1630130A1 (en) | Fuel processor and method of starting up the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: WS-REFORMER GMBH, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WUNNING, JOACHIM A.;REEL/FRAME:018272/0189 Effective date: 20060829 |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FEPP | Fee payment procedure |
Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY |
|
LAPS | Lapse for failure to pay maintenance fees |
Free format text: PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY |
|
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20211027 |